This invention relates to compositions useful in the microelectronics industry for cleaning semiconductor wafer substrates. Particularly, this invention relates to alkaline stripping or cleaning compositions containing bath stabilizing agents that are used for cleaning wafers having metal lines and vias by removing metallic and organic contamination without damaging the integrated circuits.
An integral part of microelectronic fabrication is the use of photoresists to transfer an image from a mask or reticle to the desired circuit layer. After the desired image transfer has been achieved, an etching process is used to form the desired structures. The most common structures formed in this way are metal lines and vias.
The metal lines are used to form electrical connections between various parts of the integrated circuit that lie in the same fabrication layer. The vias are holes that are etched through dielectric layers and later filled with a conductive metal. These are used to make electrical connections between different vertical layers of the integrated circuit. A halogen containing gas is generally used in the processes used for forming metal lines and vias.
After the etching process has been completed, the bulk of the photoresist may be removed by either a chemical stripper solution or by an oxygen plasma ashing process. The problem is that these etching processes produce highly insoluble metal-containing residues that may not be removed by common chemical stripper solutions. Also, during an ashing process the metal-containing residues are oxidized and made even more difficult to remove, particularly in the case of aluminum-based integrated circuits. See, xe2x80x9cManaging Etch and Implant Residue,xe2x80x9d Semiconductor International, August 1997, pages 56-63.
An example of such an etching process is the patterning of metal lines on an integrated circuit. In this process, a photoresist coating is applied over a metal film then imaged through a mask or reticle to selectively expose a pattern in the photoresist coating. The coating is developed to remove either exposed or unexposed photoresist, depending on the tone of the photoresist used, and produce a photoresist on the metal pattern. The remaining photoresist is usually hard-baked at high temperature to remove solvents and optionally to cross-link the polymer matrix. The actual metal etching step is then performed. This etching step removes metal not covered by photoresist through the action of a gaseous plasma. Removal of such metal transfers the pattern from the photoresist layer to the metal layer. The remaining photoresist is then removed (xe2x80x9cstrippedxe2x80x9d) with an organic stripper solution or with an oxygen plasma ashing procedure. The ashing procedure is often followed by a rinsing step that uses a liquid organic stripper solution. However, the stripper solutions currently available, usually alkaline stripper solutions, leave insoluble metal oxides and other metal-containing residues on the integrated circuit.
Another example of such an etching process is the patterning of vias (interconnect holes) on an integrated circuit. In this process, a photoresist coating is applied over a dielectric film then imaged through a mask or reticle to selectively expose a pattern in the photoresist coating. The coating is developed to remove either exposed or unexposed photoresist, depending on the tone of the photoresist used, and produce a photoresist on the metal pattern. The remaining photoresist is usually hard-baked at high temperature to remove solvents and optionally to cross-link the polymer matrix. The actual dielectric etching step is then performed. This etching step removes dielectric not covered by photoresist through the action of a gaseous plasma. Removal of such dielectric transfers the pattern from the photoresist layer to the dielectric layer. The remaining photoresist is then removed (xe2x80x9cstrippedxe2x80x9d) with an organic stripper solution or with an oxygen plasma ashing procedure. Typically, the dielectric is etched to a point where the underlying metal layer is exposed. A titanium or titanium nitride anti-reflective or diffusion barrier layer is typically present at the metal/dielectric boundary. This boundary layer is usually etched through to expose the underlying metal. It has been found that the action of etching through the titanium or titanium nitride layer causes titanium to be incorporated into the etching residues formed inside of the via. Oxygen plasma ashing oxidizes these via residues making them more difficult to remove.
The use of alkaline strippers on microcircuit containing metal films has not always produced quality circuits, particularly when used with metal films containing aluminum or various combinations or alloys of active metals such as aluminum or titanium with more electropositive metals such as copper or tungsten. Various types of metal corrosion, such as corrosion whiskers, pitting, notching of metal lines, have been observed due, at least in part, to reaction of the metals with alkaline strippers. Further it has been shown, by Lee et al., Proc. Interface ""89, pp. 137-149, that very little corrosive action takes place until the water rinsing step that is required to remove the organic stripper from the wafer. The corrosion is evidently a result of contacting the metals with the strongly alkaline aqueous solution that is present during rinsing. Aluminum metal is known to corrode rapidly under such conditions, Ambat et al., Corrosion Science, Vol. 33 (5), p. 684. 1992.
Prior methods used to avoid this corrosion problem employed intermediate rinses with non-alkaline organic solvents such as isopropyl alcohol. However, such methods are expensive and have unwanted safety, chemical hygiene, and environmental consequences.
The prior art discloses several organic strippers used to remove bulk photoresist after the etching process. U.S. Pat. Nos. 4,765,844, 5,102,777 and 5,308,745 disclose photoresist strippers comprising various combinations of organic solvents. These strippers, however, are not very effective on wafers that have been xe2x80x9cashedxe2x80x9d with oxygen plasmas as described above. Some photoresist strippers attempt to address this problem by adding additional water and an organic corrosion inhibitor such as catechol. Such compositions are disclosed in U.S. Pat. Nos. 5,482,566, 5,279,771, 5,381,807, 5,334,332, 5,709,756, 5,707,947, and 5,419,779 and in WO 9800244. In some cases, the hydrazine derivative, hydroxylamine, is added as well. The use of catechol or hydroxylamine in stripping compositions gives rise to various environmental, safety, and health concerns.
The use of an aqueous solution containing a quaternary ammonium hydroxide and a quaternary ammonium salt of silicic acid or alkyl silicate has been used as photoresist developers for positive tone photoresists in disclosures such as JP 1120552 (published May 12, 1989) and U.S. Pat. No. 4,628,023. Positive tone photoresist developers are used to remove patterned bulk photoresist after exposure to a solublizing radiation source. Developers are used prior to etching for pattern transfer to the exposed metal or dielectric substrate where metallic residues are generated. The object of the use of a quaternary ammonium salt of silicic acid in this disclosure is to prevent corrosion of metal substrates while removing the soluble bulk organic photoresist and not the removal of metal-rich post etch residues present on metal substrates without causing corrosion.
In U.S. Pat. Nos. 6,020,292; 5,817,610 and EP 829,768 the use of a quaternary ammonium silicate, quaternary ammonium hydroxide and water is disclosed for use in removing plasma etch residues. In U.S. Pat. No. 5,759,973 and EP 828,197 the use of a quaternary ammonium silicate, an amine compound, water and optionally an organic polar solvent is disclosed for use as a stripping and cleaning composition. In WO 9960448, many silicate containing compositions are described that effectively remove metal-containing ash residues without causing corrosion.
The use of a quaternary ammonium hydroxide in photoresist strippers is disclosed in U.S. Pat. Nos. 4,776,892, 5,563,119; JP 09319098 A2; EP 578507 A2; WO 9117484 A1 and U.S. Pat. No. 4,744,834. The use of chelating and complexing agents to sequester metals in various cleaners has also been reported in WO 9705228, U.S. Pat. Nos. 5,466,389, 5,498,293, EP 812011, U.S. Pat. No. 5,561,105, JP 06216098, JP 0641773, JP 06250400 and GB 1,573,206.
The use of an alkyl ammonium hydroxide solution containing a surfactant capable of forming a monolayer absorbed onto the sidewall of a patterned metal layer is disclosed in U.S. Pat. No. 6,057,240 for use as a post etch residue remover used in the fabrication process of a microelectonic device.
Photoresist developers containing tetramethylammonium hydroxide have also been disclosed as being useful for removing post via etch polymers in U.S. Pat. Nos. 5,412,868; 5,597,983 and EP 540261 B1.
U.S. Pat. No. 5,466,389 discloses an aqueous alkaline containing cleaning solution for microelectronics substrates that contains a quaternary ammonium hydroxide and optional metal chelating agents and is useful for a pH range of about 8 to 10. In the present invention, a pH greater than 10 is required to effect the desired residue removal.
U.S. Pat. No. 5,498,293 discloses a process for using an aqueous alkaline cleaning solution that contains a quaternary ammonium hydroxide and optional metal chelating agents useful for cleaning silicon wafers. The disclosure of this cleaning process is for treatments to substrates before the presence of integrated metal circuits and is used to generate a wafer surface that is essentially silicon dioxide free and would be employed before the use of photoresist for integrated circuit fabrication. The present invention, in contrast, focuses on the cleaning of wafers with integrated circuits present which have been photoresist coated, etched, and oxygen plasma ashed.
Although the compositions disclosed in WO 9960448 effectively remove all organic contamination and metal-containing residues remaining after a typical etching process, these compositions have a relatively short bath life. There is, therefore, a need for similar compositions with very long bath lives exceeding twenty hours.
It is, therefore, an object of the present invention to provide compositions useful in the microelectronics industry for cleaning semiconductor wafer substrates.
It is another object of the present invention to provide compositions that remove metallic and organic contamination from semiconductor wafer substrates without damaging the integrated circuits.
It is another object of the present invention to provide compositions that have very long effective bath lives.
It is a further object of the present invention to provide a method for cleaning semiconductor wafer substrates that removes metallic and organic contamination from such substrates without damaging the integrated circuits and avoiding the expense and adverse consequences caused by intermediate rinses.
These and other objects are achieved using new aqueous compositions for stripping or cleaning semiconductor wafer substrates that contain one or more metal ion-free bases and at least one bath stabilizing agent. The compositions are placed in contact with a semiconductor wafer substrate for a time and at a temperature sufficient to clean unwanted contaminants and/or residues from the substrate surface.
Preferably, the compositions contain one or more metal ion-free bases dissolved in water in sufficient amounts to produce a pH of about 10 or greater and a bath stabilizing effective amount, generally about 0.1% to about 50% by weight, of at least one bath stabilizing agent comprising at least one compound with at least one pKa in the range of 10 to 13.
Any suitable base may be used in the compositions of this invention. Preferably, the base is selected from hydroxides and organic amines, most preferably quaternary ammonium hydroxides, ammonium hydroxides and diamines.
Any suitable bath stabilizing agent comprising of at least one pKa in the range of 10 to 13 may be used in the compositions of the present invention. The bath stabilizing agents are preferably compounds with at least one pKa in the range of 11 to 12.5. The most preferable of these compounds are acetone oxime, hydrogen peroxide, salicylic acid, 5-sulfosalicylic acid, phosphoric acid, 2-hydroxypyridine, 4-hydroxypyridine, resorcinol, 2-methylresorcinol, salicylaldoxime, 2-methyl-1,5-pentanediamine, 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,3-diaminopentane and orcinol. Other examples of bath stabilizing agents with a pKa in the preferred range of 11 to 12.5 are: hydrogen germanate, adenosine, cytosine, arginine, benzil-xcex1-dioxime, benzimidazole, benzoylhydrazine, benzoylpyruvic acid, berberine, biguanide, 2-butyl-1-methyl-2-pyrroline, calmagite, chrome azurol S, chrome dark blue, cumene hydroperoxide, 1,2-cyclohexylenedinitriloacetic acid, cytidine, diethylbiguanide, diguanide, 2,4-dihydroxy-1-phenylazobenzene, 2,6-dihydroxypurine, dimethylbiguanide, ethylbiguanide, ethylenebiguanide, ethyl methyl ketoxime, 1-ethyl-2-methyl-2-pyrroline, 4-formyl-3-methoxypyridine, guanine, guanosine, 2-hydroxybenzaldehyde oxime, N-(hydroxyethyl)biguanide, 2-hydroxyquinoline, hypoxanthene, inosine, 5-iodohistamine, 2,2xe2x80x2-methylenebis(4-chlorophenol), 2-methyl-8-hydroxyquinoline, 4-methyl-8-hydroxyquinoline, 1-methylxanthine, phenylalanylarginine, silicic acid, sparteine, thorin, toluhydroquinone, tyrosylarginine, xanthosine, acetamidine, trifluoroethanol, trichloroethanol, pyridine-4-aldehyde, hypoxanthine, uric acid, pyrrolidine, diethylamine, piperidine, 3-amino-3-methylpentane, diisopropylamine, saccharin, 2,2,4-trimethylpiperidine, dibutylamine, L-3,4-dihydroxyphenylalanine, 2,2,6,6-tetramethylpiperidine, 5-hydroxytryptamine, butylcyclohexylamine, 2-phenylbenzimidazole, 2-methyl-2-butanethiol, 2-methyl-2-propanethiol, dihexylamine, methoxypyridine, 1,4-dihydroxy-2,3,5,6-tetramethylbenzene, glutarimide, malanonitrile, benzamidine, 4-hydroxyquinoline, 4,4,9,9-tetramethyl-5,8-diazododecane-2,11-diamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine 1,10-decanediamine, 1,12-dodecanediamine, hydrogen hyponitrite, hydroxylamine-N,N-disulfonic acid, (1,2-cyclohexylenedinitrilo)tetraacetic acid (CYDTA) and diethylenetriaminepenta(methylenephosphonic acid) (DETPA).
Additional examples of bath stabilizing agents with at least one pKa in the 10-11 range are: lysine, tyrosine, 3-amino-N,N-bis(2-aminoethyl)propylamine, tris(2-aminoethyl)amine, 3-(cyclohexylamino)-1-propanesulfonic acid, methylamine, dimethylamine, ethylamine, cysteamine, 1,2-ethanediamine, xcex1-alanine, xcex2-alanine, azetidine, methyiglycine, cysteine, propylamine, 1,3-propanediamine, 4-aminobutanoic acid, 2-methylalanine, homocysteine, 2,4-diaminobutanoic acid, butylamine, 1,4-butanediamine, 2,3-butanediamine, 1,2-dimethylaminoethane, proline, N-methylpyrrolidine, 5-aminopentanoic acid, N-propylglycine, ornithine, 1-amino-2,2-dimethylpropane, diethylmethylamine, 3-methyl-1-butanamine, 2-methyl-2-butanamine, 3-pentanamine, pentylamine, 1,5-pentanediamine, 2-pyridinecarboxaldehyde oxime, hydroquinone, pipecolic acid, cyclohexylamine, 1,2-dimethylpyrrolidine, 1-methylpiperidine, 6-aminohexanoic acid, hexylamine, triethylamine, cresol, 2-dimethylaminopurine, 1,2-dimethylpiperidine, 1-ethylpiperidine, 2-heptanamine, heptylamine, tyramine, dopamine, N-methyl-2-heptanamine, octylamine, 1-butylpiperidine, nonylamine, tryptamine, d-ephedrine, bornylamine, neobornylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, L-thyroxine, pentadecylamine, hexadecylamine, octadecylamine, 4-aminobutyric acid, 2-amino-2-methylpropionic acid, 3-aminopropionic acid, ethylenediaminetetraacetic acid (EDTA), N,Nxe2x80x2-dimethylethyleneamine-N,Nxe2x80x2-diacetic acid, methylaminodiacetic acid, 2-methyl-2-propylamine, nitrilotriacetic acid, 1,2,4-triazole, chloral, ethtyl acetoacetate, phenol, xcex2-phenylethylboric acid, nitromethane, thioglycollic acid, ethyl mercaptan, cyanamide, docosylamine, tert-butylamine, trimethylamine, 2-mercaptoethylamine, 5-aminovaleric acid, 4-aminophenol, hydrogen hypoiodite, aminopropylmorpholine, ethanethiol, carbonic acid, tetramethylammonium carbonate, ammonium bicarbonate, ammonium carbonate, choline bicarbonate, carbon dioxide+water, threonine, hydrogen thiophosphate, sarcosine, 4-methoxyphenol, 4-ethoxyphenol, 4-propoxyphenol, 4-butoxyphenol and 4-pentoxyphenol.
Additional examples of bath stabilizing agents with at least one pKa in the 12.5-13 range are: 5-hydroxymethylcytosine, oxaloacetic acid, cumene hydroperoxide, diguanidine, hydrogen sulfide and hydrogen peroxophosphate.
The compositions of the present invention may contain other components such as silicates, chelating agents, organic co-solvents, and surfactants. Chelating agents are preferably present in amounts up to about 2% by weight, organic co-solvents are preferably present in amounts up to about 30% by weight. The compositions can be used to clean substrates containing integrated circuits or can be used to clean substrates that do not contain integrated circuits. When integrated circuits are present, the composition removes the contaminants without damaging the integrated circuits.
The method for cleaning semiconductor wafer substrates of the present invention requires that the compositions of the present invention be placed in contact with a semiconductor wafer substrate for a time and at a temperature sufficient to clean unwanted contaminants and/or residues from the substrate surface. The method includes both bath and spray applications. Typically, the substrate is exposed to the composition for the appropriate time and at the appropriate temperature, rinsed using high purity de-ionized water, and dried.
The compositions clean wafer substrates by removing metallic and organic contamination. Importantly, the cleaning process does not damage integrated circuits on the wafer substrates and avoids the expense and adverse consequences associated with intermediate rinses required in prior methods.
Other objects, advantages, and novel features of the present invention will become apparent in the following detailed description of the invention.
The present invention provides new aqueous compositions for stripping or cleaning semiconductor wafer substrates that contain one or more metal ion-free bases and one or more bath stabilizing agents comprising a compound with at least one pKa in the range of 10-13. Preferably, the invention provides aqueous, alkaline stripping or cleaning compositions comprising one or more alkaline metal ion-free base components in an amount sufficient to produce a solution pH of about 10 or greater, preferably from about pH 11 to about pH 13, and one or more bath stabilizing agents comprising a compound with at least one pKa in the range of 10-13, preferably 11-12.5, in a concentration by weight of about 0.1% to about 50%, preferably from about 0.1% to about 35%. In formulations that contain more than about 30% total organics, the pH of the solution should be taken for a 5 wt % solution diluted in de-ionized water.
The compositions may also contain a water-soluble metal ion-free silicate in a concentration by weight of about 0.01% to 5%, and a chelating agent in a concentration by weight of about 0.01% to about 10%, generally from about 0.01% to about 2%. Further optional components are water-soluble organic solvents in a concentration by weight of about 0.1% to about 30%, preferably about 1% to about 30%, and a water-soluble surfactant in an amount by weight of about 0.01% to about 1%, preferably about 0.01% to about 0.5%.
The composition is an aqueous solution containing the base, the bath stabilizing agent, the optional components, if any, and water, preferably high purity de-ionized water.
Any suitable base may be used in the compositions of the present invention. The bases are preferably quaternary ammonium hydroxides, such as tetraalkyl ammonium hydroxides (including hydroxy- and alkoxy-containing alkyl groups generally of from 1 to 4 carbon atoms in the alkyl or alkoxy group) and diamines. The most preferable of these alkaline materials are tetramethyl ammonium hydroxide and trimethyl-2-hydroxyethyl ammonium hydroxide (choline). Examples of other usable quaternary ammonium hydroxides include: trimethyl-3-hydroxypropyl ammonium hydroxide, trimethyl-3-hydroxybutyl ammonium hydroxide, trimethyl-4-hydroxybutyl ammonium hydroxide, triethyl-2-hydroxyethyl ammonium hydroxide, tripropyl-2-hydroxyethyl ammonium hydroxide, tributyl-2-hydroxyethyl ammonium hydroxide, dimethylethyl-2-hydroxyethyl ammonium hydroxide, dimethyldi(2-hydroxyethyl) ammonium hydroxide, monomethyltriethanol ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, tetraethanol ammonium hydroxide, monomethyltriethyl ammonium hydroxide, monomethyltripropyl ammonium hydroxide, monomethyltributyl ammonium hydroxide, monoethyltrimethyl ammonium hydroxide, monoethyltributyl ammonium hydroxide, dimethyldiethyl ammonium hydroxide, dimethyldibutyl ammonium hydroxide, and the like and mixtures thereof.
Other bases that will function in the present invention include ammonium hydroxide, organic amines particularly alkanolamines such as 2-aminoethanol, 1-amino-2-propanol, 1-amino-3-propanol, 2-(2-aminoethoxy)ethanol, 2-(2-aminoethylamino)ethanol, 2-(2-aminoethylamino)ethylamine and the like, and other strong organic bases such as guanidine, 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 1,3-pentanediamine, 4-aminomethyl-1,8-octanediamine, aminoethylpiperazine, 4-(3-aminopropyl)morpholine, 1,2-diaminocyclohexane, tris(2-aminoethyl)amine, 2-methyl-1,5-pentanediamine and hydroxylamine. Alkaline solutions containing metal ions such as sodium or potassium may also be operative, but are not preferred because of the possible residual metal contamination that could occur. Mixtures of these additional alkaline components, particularly ammonium hydroxide, with the aforementioned tetraalkyl ammonium hydroxides are also useful.
Any suitable bath stabilizing agent comprising a compound having at least one pKa in the range of 10 to 13, may be used in the compositions of the present invention. The bath stabilizing agents are preferably compounds with at least one pKa in the range of 11 to 12.5. The most preferable of these compounds are acetone oxime, hydrogen peroxide, salicylic acid, 5-sulfosalicylic acid, phosphoric acid, 2-hydroxypyridine, 4-hydroxypyridine, resorcinol, 2-methylresorcinol, salicylaldoxime, 2-methyl-1,5-pentanediamine, 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,12-dodecanediamine, 1,3-diaminopentane and orcinol, but are not limited to, those listed herein before in the Summary Of the Invention section. Additional suitable bath stabilizing agents having at least one pKa value of from 10 to 13 can be found listed in xe2x80x9cLange""s Handbook of Chemistryxe2x80x9d, 15th Edition, Section 8, pages 8-24 to 8-79, by J. Dean, xe2x80x9cThe Determination of Ionization Constants, A Laboratory Manualxe2x80x9d by A. Albert and E. Serjeant, 2nd edition, Chapters 6 to 9, pages 72-107, and the xe2x80x9cCRC Handbook of Chemistry and Physicsxe2x80x9d, 78th Edition, pages 7-1 to 7-3, 7-6 and 8-43 to 8-55, by D. Lide. Additional compounds with at least one pKa in the 10-13 range can also be found in the computer software programs xe2x80x9cNIST Standard Reference Database 46: NIST Critically Selected Stability Constants of metal Complexes Databasexe2x80x9d available from NIST and the program xe2x80x9cACD/pKa DBxe2x80x9d that is available from Advanced Chemistry Development, Inc. of Toronto, Canada. ACD/pKa DB also allows predictions of pKa""s from structures. The compounds having at least one pKa in the range of 10-13 useful as bath stabilization agents for this invention are those that when incorporated into a composition for stripping or cleaning integrated circuit substrates provide compositions that evidence less pH drop on aging of the composition compared to an identical composition without the bath stabilization agent. Mixtures of suitable bath stabilizing agents may be used.
Any suitable metal ion-free silicate may be used in the compositions of the present invention. The silicates are preferably quaternary ammonium silicates, such as tetraalkyl ammonium silicate (including hydroxy- and alkoxy-containing alkyl groups generally of from 1 to 4 carbon atoms in the alkyl or alkoxy group). The most preferable metal ion-free silicate component is tetramethyl ammonium silicate. Other suitable metal ion-free silicate sources for this invention may be generated in-situ by dissolving any one or more of the following materials in the highly alkaline cleaner. Suitable metal ion-free materials useful for generating silicates in the cleaner are solid silicon wafers, silicic acid, colloidal silica, fumed silica or any other suitable form of silicon or silica. Metal silicates such as sodium metasilicate may be used but are not recommended due to the detrimental effects of metallic contamination on integrated circuits.
The compositions of the present invention may also be formulated with suitable metal chelating or complexing agents to increase the capacity of the formulation to retain metals in solution and to enhance the dissolution of metallic residues on the wafer substrate. Typical examples of chelating agents useful for this purpose are the following organic acids and their isomers and salts: (ethylenedinitrilo)tetraacetic acid (EDTA), butylenediaminetetraacetic acid, (1,2-cyclohexylenedinitrilo)tetraacetic acid (CyDTA), diethylenetriaminepentaacetic acid, ethylenediaminetetrapropionic acid, (hydroxyethyl)ethylenediaminetriacetic acid (HEDTA), N,N,Nxe2x80x2,Nxe2x80x2-ethylenediaminetetra(methylenephosphonic)acid (EDTMP), triethylenetetraminehexaacetic acid (TTHA), 1,3-diamino-2-hydroxypropane-N,N,Nxe2x80x2,Nxe2x80x2-tetraacetic acid (DHPTA), methyliminodiacetic acid, propylenediaminetetraacetic acid, 1,5,9-triazacyclododecane-N,Nxe2x80x2,Nxe2x80x3-tris(methylenephosphonic acid) (DOTRP), 1,4,7,10-tetraazacyclododecane-N,Nxe2x80x2,Nxe2x80x3,Nxe2x80x2xe2x80x3-tetrakis(methylenephosphonic acid) (DOTP), nitrilotris(methylene)triphosphonic acid, diethylenetriaminepenta(methylenephosphonic acid) (DETAP), aminotri(methylenephosphonic acid), 1-hydroxyethylene-1,1-diphosphonic acid, bis(hexamethylene)triamine phosphonic acid, 1,4,7-triazacyclononane-N,Nxe2x80x2,Nxe2x80x3-tris(methylenephosphonic acid (NOTP), 2-phosphonobutane-1,2,4-tricarboxylic acid, nitrolotriacetic acid (NTA), citric acid, tartaric acid, gluconic acid, saccharic acid, glyceric acid, oxalic acid, phthalic acid, maleic acid, mandelic acid, malonic acid, lactic acid, salicylic acid, 5-sulfosalicylic acid, catechol, gallic acid, propyl gallate, pyrogallol, 8-hydroxyquinoline, and cysteine. Examples of complexing agents are phosphoric acid, nitric acid, sulfuric acid, hydrochloric acid and hydrofluoric acid. A phosphonic acid or CyDTA chelating agent is preferably employed when the composition contains an oxidizing bath stabilizing agent, such as hydrogen peroxide. Chelating agents such as EDTA are not nearly as oxidation resistant as CyDTA and phosphonic acid chelating agents.
Preferred chelating agents are aminocarboxylic acids such as EDTA or CyDTA and phosphonic acids. Many aminocarboxylic acids and phosphonic acid chelating agents have at least one pKa in the 10-13 range. Chelating agents of this class have a high affinity for the aluminum-containing residues typically found on metal lines and vias after plasma xe2x80x9cashingxe2x80x9d. In addition, the pKa""s for this class of chelating agents typically include one pKa of approximately 12 which improves the performance of the compositions of the invention.
The compositions of the present invention may also contain one or more suitable water-soluble organic solvents. Among the various organic solvents suitable are alcohols, polyhydroxy alcohols, glycols, glycol ethers, alkyl-pyrrolidinones such as N-methylpyrrolidinone (NMP), 1-hydroxyalkyl-2-pyrrolidinones such as 1-(2-hydroxyethyl)-2-pyrrolidinone (HEP), dimethylformamide (DMF), dimethylacetamide (DMAc), sulfolane, dimethyl-2-piperidone (DMPD) or dimethylsulfoxide (DMSO). These solvents may be added to reduce aluminum and/or aluminum-copper alloy and/or copper corrosion rates if further aluminum and/or aluminum-copper alloy and/or copper corrosion inhibition is desired. Preferred water-soluble organic solvents are polyhydroxy alcohols such as glycerol and/or 1-hydroxyalkyl-2-pyrrolidinones such as 1-(2-hydroxyethyl)-2-pyrrolidinone (HEP).
The compositions of the present invention may also contain any suitable water-soluble amphoteric, non-ionic, cationic or anionic surfactant. The addition of a surfactant will reduce the surface tension of the formulation and improve the wetting of the surface to be cleaned and therefore improve the cleaning action of the composition. The surfactant may also be added to reduce aluminum corrosion rates if further aluminum corrosion inhibition is desired.
Amphoteric surfactants useful in the compositions of the present invention include betaines and sulfobetaines such as alkyl betaines, amidoalkyl betaines, alkyl sulfobetaines and amidoalkyl sulfobetaines; aminocarboxylic acid derivatives such as amphoglycinates, amphopropionates, amphodiglycinates, and amphodipropionates; iminodiacids such as alkoxyalkyl iminodiacids or alkoxyalkyl iminodiacids; amine oxides such as alkyl amine oxides and alkylamido alkylamine oxides; fluoroalkyl sulfonates and fluorinated alkyl amphoterics; and mixtures thereof.
Preferably, the amphoteric surfactants are cocoamidopropyl betaine, cocoamidopropyl dimethyl betaine, cocoamidopropyl hydroxy sultaine, capryloamphodipropionate, cocoamidodipropionate, cocoamphopropionate, cocoamphohydroxyethyl propionate, isodecyloxypropylimino dipropionic acid, laurylimino dipropionate, cocoamidopropylamine oxide and cocoamine oxide and fluorinated alkyl amphoterics.
Non-ionic surfactants useful in the compositions of the present invention include acetylenic diols, ethoxylated acetylenic diols, fluorinated alkyl alkoxylates, fluorinated alkylesters, fluorinated polyoxyethylene alkanols, aliphatic acid esters of polyhydric alcohols, polyoxyethylene monoalkyl ethers, polyoxyethylene diols, siloxane type surfactants, and alkylene glycol monoalkyl ethers. Preferably, the non-ionic surfactants are acetylenic diols or ethoxylated acetylenic diols.
Anionic surfactants useful in the compositions of the present invention include carboxylates, N-acylsarcosinates, sulfonates, sulfates, and mono and diesters of orthophosphoric acid such as decyl phosphate. Preferably, the anionic surfactants are metal-free surfactants.
Cationic surfactants useful in the compositions of the present invention include amine ethoxylates, dialkyldimethylammonium salts, dialkylmorpholinum salts, alkylbenzyldimethylammonium salts, alkyltrimethylammonium salts, and alkylpyridinium salts. Preferably, the cationic surfactants are halogen-free surfactants.
In a preferred embodiment of the present invention, the composition is an aqueous solution containing about 0.1-25%, more preferably about 0.1-12%, by weight tetramethylammonium hydroxide (TMAH) and about 0.1% to about 35% by weight sulfosalicylic acid, phosphoric acid, hydrogen peroxide, 2-hydroxypyridine, 4-hydroxypyridine, resorcinol or 2-methylresircinol.
In another embodiment of the present invention, the composition is an aqueous solution containing about 0.1-5% by weight tetramethylammonium hydroxide (TMAH), about 0.1% to about 3% by weight sulfosalicylic acid or phosphoric acid, about 0.01-1% by weight trans-(1,2-cyclohexylenedinitrilo)tetraacetic acid (CyDTA), and about 0-1% by weight (calculated as % SiO2) tetramethylammonium silicate (TMAS).
In another embodiment of the present invention, the composition is an aqueous solution containing about 0.1-5% by weight tetramethylammonium hydroxide (TMAH), about 0.01-1% by weight trans-(1,2-cyclohexylenedinitrilo)tetraacetic acid (CyDTA), about 0.1% to about 3% by weight sulfosalicylic acid or phosphoric acid, about 0-1% by weight (calculated as % SiO2) tetramethylammonium silicate (TMAS), and about 0.5-30% by weight of polyhydroxy compounds, preferably glycerol.
In another embodiment of the present invention, the composition is an aqueous solution containing about 0.1-3% by weight tetramethylammonium hydroxide (TMAH), about 0.1% to about 3% by weight sulfosalicylic acid or phosphoric acid, about 0.01-1% by weight trans-(1,2-cyclohexylenedinitrilo)tetraacetic acid (CyDTA), about 0-1% by weight (calculated as % SiO2) tetramethylammonium silicate (TMAS), about 0.5-30% by weight of polyhydroxy compounds, and about 0.01-0.3% by weight of a nonionic ethoxylated acetylenic diol surfactant.
In another embodiment of the present invention, the composition is an aqueous solution containing about 0.1-5% by weight tetramethylammonium hydroxide (TMAH), about 0.1% to about 3% by weight hydrogen peroxide or salicylic acid, about 0.01-1% by weight trans-(1,2-cyclohexylenedinitrilo)tetraacetic acid (CyDTA), and about 0-1% by weight (calculated as % SiO2) tetramethylammonium silicate (TMAS).
In another embodiment of the present invention, the composition is an aqueous solution containing about 0.1-5% by weight tetramethylammonium hydroxide (TMAH), about 0.01-1% by weight trans-(1,2-cyclohexylenedinitrilo)tetraacetic acid (CyDTA), about 0.1% to about 3% by weight hydrogen peroxide or salicylic acid, about 0-1% by weight (calculated as % SiO2) tetramethylammonium silicate (TMAS), and about 0.5-30% by weight of polyhydroxy compounds, preferably glycerol.
In another embodiment of the present invention, the composition is an aqueous solution containing about 0.1-3% by weight tetramethylammonium hydroxide (TMAH), about 0.1% to about 3% by weight hydrogen peroxide or salicylic acid, about 0.01-1% by weight trans-(1,2-cyclohexylenedinitrilo)tetraacetic acid (CyDTA), about 0-1% by weight (calculated as % SiO2) tetramethylammonium silicate (TMAS), about 0.5-30% by weight of polyhydroxy compounds, and about 0.01-0.3% by weight of a nonionic ethoxylated acetylenic diol surfactant.
In another embodiment of the present invention, the composition is an aqueous solution containing about 0.1-2% by weight tetramethylammonium hydroxide (TMAH), about 0.01-1% by weight trans-(1,2-cyclohexylenedinitrilo)tetraacetic acid (CyDTA), about 0-1% by weight (calculated as % SiO2) tetramethylammonium silicate (TMAS), about 0.1% to about 3% by weight hydrogen peroxide or salicylic acid and about 0.5-30% by weight of an alkyl-pyrrolidinone such as 1-(2-hydroxyethyl)-2-pyrrolidinone (HEP), preferably 1-(2-hydroxyethyl)-2-pyrrolidinone (HEP).
In another embodiment of the present invention, the composition is an aqueous solution containing about 0.1-2% by weight tetramethylammonium hydroxide (TMAH), about 0.01-1% by weight trans-(1,2-cyclohexylenedinitrilo)tetraacetic acid (CyDTA), about 0-1% by weight (calculated as % SiO2) tetramethylammonium silicate (TMAS), about 0.1% to about 3% by weight hydrogen peroxide or salicylic acid, about 0.5-30% by weight of an alkyl-pyrrolidinone such as 1-(2-hydroxyethyl)-2-pyrrolidinone (HEP), and about 0.01-0.3% by weight of a nonionic ethoxylated acetylenic diol surfactant.
In another embodiment of the present invention, the composition is an aqueous solution containing about 0.1-2% by weight tetramethylammonium hydroxide (TMAH), about 0.01-1% by weight trans-(1,2-cyclohexylenedinitrilo)tetraacetic acid (CyDTA), about 0.1% to about 3% by weight sulfosalicylic acid or phosphoric acid, about 0-1% by weight (calculated as % SiO2) tetramethylammonium silicate (TMAS), and about 0.5-30% by weight of an alkyl-pyrrolidinone such as 1-(2-hydroxyethyl)-2-pyrrolidinone (HEP), preferably 1-(2-hydroxyethyl)-2-pyrrolidinone (HEP).
In another embodiment of the present invention, the composition is an aqueous solution containing about 0.1-2% by weight tetramethylammonium hydroxide (TMAH), about 0.01-1% by weight trans-(1,2-cyclohexylenedinitrilo)tetraacetic acid (CyDTA), about 0.1% to about 3% by weight sulfosalicylic acid or phosphoric acid, about 0-1% by weight (calculated as % SiO2) tetramethylammonium silicate (TMAS), about 0.5-30% by weight of an alkyl-pyrrolidinone such as 1-(2-hydroxyethyl)-2-pyrrolidinone (HEP), and about 0.01-0.3% by weight of a nonionic ethoxylated acetylenic diol surfactant.
In another embodiment of the present invention, the composition is an aqueous solution containing about 0.1-5% by weight tetramethylammonium hydroxide (TMAH), about 0.01-1% by weight diethylenetriaminepenta(methylenephosphonic acid), about 0.1% to about 3% by weight hydrogen peroxide and about 0-1% by weight (calculated as % SiO2) tetramethylammonium silicate (TMAS).
In another embodiment of the present invention, the composition is an aqueous solution containing about 0.1-25% by weight tetramethylammonium hydroxide (TMAH), about 0.1% to about 20% by weight hydroxylamine, about 0.1% to about 35% by weight 2-hydroxypyridine or 4-hydroxypyridine, about 0-1% by weight trans-(1,2-cyclohexylenedinitrilo)tetraacetic acid (CyDTA), about 0-1% by weight (calculated as % SiO2) tetramethylammonium silicate (TMAS) and about 0-0.3% by weight of a nonionic ethoxylated acetylenic diol surfactant.
In another embodiment of the present invention, the composition is an aqueous solution containing about 0.1-10% by weight tetramethylammonium hydroxide (TMAH), about 0.1% to about 15% by weight 2-hydroxypyridine, about 0-1% by weight trans-(1,2-cyclohexylenedinitrilo)tetraacetic acid (CyDTA), about 0-1% by weight (calculated as % SiO2) tetramethylammonium silicate (TMAS), about 0-30% by weight of polyhydroxy compounds, and about 0-0.3% by weight of a nonionic ethoxylated acetylenic diol surfactant.
In another embodiment of the present invention, the composition is an aqueous solution containing about 0.1-10% by weight tetramethylammonium hydroxide (TMAH), about 0.1% to about 15% by weight 4-hydroxypyridine, about 0-1% by weight trans-(1,2-cyclohexylenedinitrilo)tetraacetic acid (CyDTA), about 0-1% by weight (calculated as % SiO2) tetramethylammonium silicate (TMAS), about 0-30% by weight of polyhydroxy compounds, and about 0-0.3% by weight of a nonionic ethoxylated acetylenic diol surfactant.
In another embodiment of the present invention, the composition is an aqueous solution containing about 0.1-25% by weight tetramethylammonium hydroxide (TMAH), about 0.1% to about 15% by weight resorcinol, about 0-1% by weight trans-(1,2-cyclohexylenedinitrilo)tetraacetic acid (CyDTA), about 0-2% by weight (calculated as % SiO2) tetramethylammonium silicate (TMAS), about 0-30% by weight of polyhydroxy compounds, and about 0-0.3% by weight of a nonionic ethoxylated acetylenic diol surfactant.
In another embodiment of the present invention, the composition is an aqueous solution containing about 0.1-4% by weight tetramethylammonium hydroxide (TMAH), about 0.1% to about 4% by weight 2-methylresorcinol, about 0-1% by weight trans-(1,2-cyclohexylenedinitrilo)tetraacetic acid (CyDTA), about 0-2% by weight (calculated as % SiO2) tetramethylammonium silicate (TMAS), about 0-30% by weight of polyhydroxy compounds, and about 0-0.3% by weight of a nonionic ethoxylated acetylenic diol surfactant.
In another embodiment of the present invention, the composition is an aqueous solution containing about 0.1-4% by weight tetramethylammonium hydroxide (TMAH), about 0.1% to about 4% by weight orcinol, about 0-1% by weight trans-(1,2-cyclohexylenedinitrilo)tetraacetic acid (CyDTA), about 0-2% by weight (calculated as % SiO2) tetramethylammonium silicate (TMAS), about 0-30% by weight of polyhydroxy compounds, and about 0-0.3% by weight of a nonionic ethoxylated acetylenic diol surfactant.
In another embodiment of the present invention, the composition is an aqueous solution containing about 0.1-10% by weight tetramethylammonium hydroxide (TMAH), about 0.1% to about 15% by weight 2-hydroxypyridine, about 0-1% by weight (calculated as % SiO2) tetramethylammonium silicate (TMAS), about 0-30% by weight of polyhydroxy compounds, and about 0-0.3% by weight of a nonionic ethoxylated acetylenic diol surfactant.
In another embodiment of the present invention, the composition is an aqueous solution containing about 0.1-10% by weight tetramethylammonium hydroxide (TMAH), about 0.1% to about 15% by weight 4-hydroxypyridine, about 0-1% by weight (calculated as % SiO2) tetramethylammonium silicate (TMAS), about 0-30% by weight of polyhydroxy compounds, and about 0-0.3% by weight of a nonionic ethoxylated acetylenic diol surfactant.
In another embodiment of the present invention, the composition is an aqueous solution containing about 0.1-10% by weight tetramethylammonium hydroxide (TMAH), about 0.1% to about 15% by weight 2-hydroxypyridine, about 0-1% by weight (calculated as % SiO2) tetramethylammonium silicate (TMAS) and about 0-30% by weight of polyhydroxy compounds.
In another embodiment of the present invention, the composition is an aqueous solution containing about 0.1-10% by weight tetramethylammonium hydroxide (TMAH), about 0.1% to about 15% by weight 4-hydroxypyridine, about 0-1% by weight (calculated as % SiO2) tetramethylammonium silicate (TMAS) and about 0-30% by weight of polyhydroxy compounds.
In all the embodiments, the balance of the composition is made up with water, preferably high purity de-ionized water.
The method of the present invention cleans semiconductor wafer substrates by exposing the contaminated substrate to the compositions of the present invention for a time and at a temperature sufficient to clean unwanted contaminants from the substrate surface. Optionally, the substrate is rinsed to remove the composition and the contaminants and dried to remove any excess solvents or rinsing agents. The substrate can then be used for its intended purpose.
Preferably, the method uses a bath or spray application to expose the substrate to the composition. Bath or spray cleaning times are generally 1 minute to 30 minutes, preferably 5 minutes to 20 minutes. Bath or spray cleaning temperatures are generally 10xc2x0 C. to 85xc2x0 C., preferably 20xc2x0 C. to 65xc2x0 C.
If required, the rinse times are generally 10 seconds to 5 minutes at room temperature, preferably 30 seconds to 2 minutes at room temperature. Preferably de-ionized water is used to rinse the substrates.
If required, drying the substrate can be accomplished using any combination of air-evaporation, heat, spinning, or pressurized gas. The preferred drying technique is spinning under a filtered inert gas flow, such as nitrogen, for a period of time until the wafer substrate is dry.
The method of the present invention is very effective for cleaning semiconductor wafer substrates that have been previously oxygen plasma ashed to remove bulk photoresist, particularly wafer substrates containing a silicon, silicon oxide, silicon nitride, tungsten, tungsten alloy, titanium, titanium alloy, tantalum, tantalum alloy, copper, copper alloy, aluminum or aluminum alloy film. The method removes unwanted metallic and organic contaminants but does not cause unacceptable corrosion to the silicon, silicon oxide, silicon nitride, tungsten, tungsten alloy, titanium, titanium alloy, tantalum, tantalum alloy, copper, copper alloy, aluminum or aluminum alloy film.
The following examples illustrate the specific embodiment of the invention described in this document. As would be apparent to skilled artisans, various changes and modifications are possible and are contemplated within the scope of the invention described.